NO310420B1 - Graft copolymers unsaturated monomers and polyhydroxy compounds, process for preparation, use of polymers - Google Patents

Abstract

PCT No. PCT/EP94/04187 Sec. 371 Date Feb. 28, 1995 Sec. 102(e) Date Feb. 28, 1995 PCT Filed Dec. 16, 1994 PCT Pub. No. WO95/17444 PCT Pub. Date Jun. 29, 1995The present invention relates to water-soluble, acid groups-containing graft copolymers which are at least partially biodegradable and are based on polyhydroxy compounds and monoethylenically unsaturated carboxylic acids, sulfonic acids and/or phosphonic acids or the salts of said acids as well as optional further monomers. The present invention further relates to a process for producing said graft copolymers at temperatures of up to 200 DEG C. by means of radical polymerization initiators, in that a total mixture is polymerized which consists of 1-60%-wt. of polyhydroxy compounds, their derivatives or their mixtures, and 95-40%-wt. of a monomer mixture comprising at least one monoethylenically unsaturated carboxylic acid, at least one monoethylenically unsaturated sulfonic acid, one monoethylenically unsaturated sulfuric acid ester and/or vinylphosphonic acid or the salts of said acids with monovalent cations, as well as optional further monomers. The present invention further relates to the use of the graft copolymers in aqueous systems, for binding multivalent metal ions, inhibiting the water hardness, as additive in detergents and cleaning agents, as textile auxiliary, dispersing agent, in particular for pigments, and as auxiliary agent in the production of paper and leather.

Description

The present invention relates to water-soluble, acid group-containing graft copolymers which are at least partially biodegradable, and which are based on polyhydroxy compounds and monoethylenically unsaturated carboxylic acids, as well as any additional monomers. The present invention further relates to a method for producing these and using them in aqueous systems. This includes, for example, the inhibition of negative effects of water hardness, the dispersing effect for pigments, use in washing liquids and dye baths, as well as use as aids in the production of paper and leather.

In such applications of the water-soluble polymers, it is important to complex multivalent metal ions to prevent precipitation of hardness elements in the water, to disperse pigments in high concentration at low viscosity or to suspend dirt particles during washing processes and prevent them from being redeposited on the textiles.

As ecological considerations have increasingly come to the fore in recent years, a large part of the efforts regarding the development of new polymers have been focused on the polymers' biological degradability. In this context, products where use and disposal take place in aqueous systems are particularly in the foreground. Within some areas, e.g. in the paper industry, degradable polymers, such as starches, have therefore more often been used as binders, and in other areas graft polymers have been developed from reproducible raw materials, such as starch or sugar, and from synthetic monomers. For many applications, however, the technical requirements are relatively high and cannot be satisfied by products based on renewable raw materials in the same way as the purely synthetic polymers used until now can. For example, the use of polycarboxylates in mixed adhesives for textile fibers can be mentioned, where a mixture of starch and polycarboxylate is often used as a compromise between degradability and gluing properties.

Another important area of application for water-soluble polymers is detergents and cleaning agents. In recent years, developments in this area have been characterized by the fact that the polyphosphate components have been replaced, as these, as is known, lead to an over-fertilization of the waterways and to the problems known as "eutrophication".

In addition to the primary washing effect, polyphosphates also have a beneficial secondary washing effect, as they remove alkaline earth metal ions from the washing water, the textiles and the dirt, prevent precipitation of insoluble alkaline earth metal salts on the textiles and keep the dirt dispersed in the washing liquid. In this way, scale deposits and graying are suppressed, even after several washing cycles. Polycarboxylates, such as polyacrylic acids and acrylic acid/maleic acid copolymers, are currently used as substitutes for polyphosphates, due to the good binding capacity for alkaline earth metal ions and due to the dispersing properties for lime, and which are characterized by the so-called Hampshire test or modifications of this according to Richter-Winkler [Richter, Winkler in Tenside Surfactants Detergents 24 (1987) 4].

In addition to this calcium-binding capacity and dispersing properties, the hydrophilic suspending capacity according to K. Schulze, G. Schreier "Die Photometrische Bestimmung des hydrophilen Suspendiervermogens - ein Beitrag zur Beurteilung des Schmutztragevermogens in Waschflotten"

(Huls Information, Chemische Werke Hiils AG) of particular importance for washing processes. The hydrophilic suspending capacity is a standard for the soil carrying capacity of detergent builders and is determined by turbidity measurements in an iron oxide suspension. The polycarboxylates currently commercially available have a very poor suspending capacity that is 10 to 20 times less than that of sodium tripolyphosphate.

The eutrophication problem could be solved by using polycarboxylates. However, biological degradation of these polymers only takes place to a very limited extent, as the degradation rates stated in the literature are between 1 and 10%. The information about this can be found in the publications by J. Lester et al. "The Partitioning of Polycarboxylic Acids in Activated Sludge", Chemosphere, vol. 21, no. 4-5, pp. 443-450 (1990), H. Schumann "Elimination von <14>C-markierten Polyelektrolyten i biologischen Abwasserreinigungsprozeszen, Wasser - Abwasser (1991), pp. 376-383, P. Berth "Moglichkei-ten und Grenzen des Ersatzes von Phosphaten in Waschmit-teln", Angewandte Chemie (1975), pp. 115-142.

From an ecological point of view, the input of large amounts of non-degradable compounds into the environment is critical. As a solution to this problem, it is therefore obvious to use biodegradable polymers, i.e. those which are decomposable into carbon dioxide and water.

Polyhydroxy compounds of the type glycerols, polysaccharides and polyvinyl alcohols are perfect products in terms of their known biological degradability, but their application technical properties are insufficient. For this reason, efforts have been made to improve the properties of these polyhydroxy compounds by modification. EP-0 427 349 A2 describes e.g. incorporation of carboxyl groups into polysaccharides by oxidation.

The calcium-binding capacity of the polysaccharides modified in this way is improved, but it does not reach the level of synthetic polycarboxylates. On the one hand, the polysaccharide's calcium-binding capacity increases, but on the other hand, it loses part of its original biological degradability. The graft copolymerization of carbohydrates and unsaturated carboxyl group-containing monomers provides an alternative to the synthesis of at least partially degradable water-soluble polymers.

EP-0 324 595 A2 describes polyacrylate-free cow builders formed by a very complicated multi-step modification of

polyhydroxy compounds, e.g. based on polyvinyl alcohol. The polyhydroxy compounds are esterified in the presence of catalyst with an excess of maleic anhydride in anhydrous, organic solvents, unreacted chemicals are separated and a further reaction with aminocarboxylic acids is carried out, and to obtain a compound that is purified from by-products, precipitation reactions are carried out again in organic solvents. These products represent neither a technical nor an economic solution for pulp products to be used in detergents. This is due to the indicated long reaction times of up to 48 hours, the complicated production method and the tendency to hydrolysis. In addition, the product must not

come into direct contact with alkaline or acidic detergent components due to the aforementioned tendency to hydrolysis.

Copolymers of unsaturated carboxylic acids with monosaccharides which are capable of forming enolates in alkaline solutions are known from DE-3 714 732 C2. They are partially biodegradable, and the binding capacity for CaCC>3 is said to be within the range of commercial polyacrylates. Glucose, fructose, mannose, maltose, xylose and galactose are primarily mentioned as useful monosaccharides capable of forming enolates. The production methods involve high technical costs and are complicated, as the end product in this production process is sediments resulting from the acid precipitation, but not the original polymer solution. Furthermore, the precipitated polymers appear as a slimy sediment that is difficult to isolate and in a form that is difficult to separate.

Radically initiated graft copolymers of mono-, oligo- or polysaccharides with a combination of unsaturated mono- and dicarboxylic acids used as detergent additives are known from DE-4 003 172 A1. They are said to be at least partially biodegradable. In addition, the graft polymers are attributed to having a comparable or better scale-inhibiting effect in textile detergents compared to this property for the known saccharide-free polymers of unsaturated mono- and dicarboxylic acids, e.g. described in EP-0 025 551 Bl. As known to those skilled in the art, the dicarboxylic acids specified as a formulation component in DE-4 003 172 A1 are difficult to polymerise; in addition, the partial loss of carboxyl groups caused by the escape of carbon dioxide during polymerization is another disadvantage. The aforementioned carbon dioxide release is described in the literature, e.g. by Braun in Makromol. Chemie 96 (1966) 100-121, and by Tate in Makromol. Chemistry 109 (1967) 176-193; it means that the process involves a financial loss. In addition, the polyelectrolyte is less efficient due to the partial loss of the carboxyl groups. Although the polymers according to DE-4 003 172 A1 are eliminated by sewage sludge, there are no clear indications regarding their biodegradability.

In Japanese patent application No. JP-A-61-31497, the use of a graft polymer as a biodegradable detergent component is described. Said graft polymers are composed of starch-type, dextrin-type or cellulose-type polysaccharides, and water-soluble monomers; water-soluble monomers with carboxyl groups are preferred, with particular preference for (meth)-acrylic acid, itaconic acid, maleic acid or fumaric acid. Graft polymers of dextrin and acrylic acid are described in the application's examples, and the dextrin content amounts to 67-34% by weight. The biodegradability was tested according to the MITI guidelines; it was in the range between 42 and 10%, i.e. below the content of the natural material in the graft polymer. There is no indication regarding the calcium-binding ability and the resistance to hard water. Despite a very large amount of graft polymer of 20% by weight, the cleaning efficiency of a detergent containing said graft polymers only came up to the level of a comparison detergent containing zeolite in an amount corresponding to the amount of the graft polymer.

In EP-0 465 287 Al, a detergent mixture is described which, among other things, comprises a graft polymer as a building agent; this is composed of synthetic polydextrose and an unsaturated water-soluble monomer. Express preference is given to the monomers (meth)-acrylic acid alone or in combination with maleic acid or itaconic acid. The examples mention exclusively graft polymers of polydextrose and acrylic acid. In a washing test carried out in comparison with zeolite, the scale reduction was 46%. This is far worse than the results obtained in washing tests with the graft polymers according to DE-4 003 172 A1, in that scale inhibition of up to 57% was achieved here.

The graft polymers according to EP-0 465 287 A1 and JP-A-61-31497 therefore have a poor detergent effect compared to the polymers according to DE-4 003 172 A1. There are no comparable data available to make an assessment regarding the calcium binding capacity or inhibition of hard water constituents for the described graft polymers. However, since both properties have a significant influence on the detergent effect, it can be assumed that the polymers according to DE-4 003 172 A1 are also superior in this regard.

According to this, the object of the present invention is to produce graft copolymers with polyhydroxy compounds by means of a simple technical process while avoiding decarboxylating monomers, the graft copolymers having an improved hydrophilic suspension capacity and an increased effect with regard to the property for complex formation of polyvalent metal ions. In addition, they are good inhibitors of water hardness and have dispersing properties for substances in aqueous systems.

According to the present invention, this purpose is achieved by means of a water-soluble graft copolymer of polyhydroxy compounds, reaction products thereof and/or derivatives thereof, with the exception of mono- and disaccharides, and oligosaccharides having an average degree of polymerization of from 1.1 to 20, sorbitol, tartaric acid and gluconic acid, and a monomer mixture obtained by radical graft copolymerization of a monomer mixture consisting of

A) 45-96% by weight of at least one monoethylenically unsaturated C3-C10 monocarboxylic acid and/or at least one salt of such

monocarboxylic acid with a monovalent cation,

B) 4-55% by weight of at least one monoethylenically unsaturated, sulfonic acid group-containing monomer, one monoethylenically unsaturated sulfuric acid ester, and/or vinylphosphonic acid and/or

at least one salt of these acids with monovalent cations, C) 0-30% by weight of at least one water-soluble, monoethylenically unsaturated compound modified with 2-50 mol of alkylene oxide per mol, D) 0-45% by weight of at least one additional water-soluble, free-radically polymerizable monomer; E) 0-30% by weight of other radically polymerizable monomers that are slightly soluble or insoluble in water,

wherein the sum of A to E amounts to 100% by weight, by avoiding decarboxylating monomers, in the presence of polyhydroxy compounds and/or the reaction products thereof and/or derivatives thereof and/or mixtures thereof, wherein the content of the polyhydroxy compounds and/or derivatives thereof and/or the reaction products of these in the total

mixture constitutes 1-60% by weight, preferably 5-40% by weight and most preferably 5-30% by weight.

Furthermore, the present invention also describes a method for the production of graft copolymers according to claims 1-9 of polyhydroxy compounds, reaction products thereof and/or derivatives thereof, and monoethylenically unsaturated monomers in solution or suspension at temperatures up to 200°C, using of free-radical polymerization initiators, characterized by the fact that a total mixture is used which consists of 1-60% by weight, preferably 5-40% by weight and most preferably 5-30% by weight polyhydroxy compounds, the reaction products and/or derivatives thereof, and 95-40% by weight of a monomer mixture consisting of

A) 45-96% by weight of at least one monoethylenically unsaturated C3-C10 monocarboxylic acid and/or at least one salt of such

monocarboxylic acid with monovalent cations,

B) 4-55% by weight of at least one monoethylenically unsaturated, sulfonic acid group-containing monomer, one monoethylenically unsaturated sulfuric acid ester, and/or vinylphosphonic acid and/or

the salts of these acids with monovalent cations,

C) 0-30% by weight of at least one water-soluble, monoethylenically unsaturated compound modified with 2-50 mol of alkylene oxide per mol, D) 0-45% by weight of at least one further water-soluble, radically polymerizable monomer, E) 0-30% by weight of other radically polymerizable monomers which are slightly soluble or insoluble in water,

the sum of A to E being 100% by weight, and for the polymerization the components in the total mixture of polyhydroxy components and monoethylenically unsaturated monomers are prepared either as a whole or in portions, and the remainder is measured or all components are measured.

According to the present invention, polyhydroxy compounds are mono-, di- and oligoglycerols and polymeric glycerols or mixtures thereof, partially or completely saponified polyvinyl alcohols resulting from polyvinyl esters or polyvinyl ethers or from vinyl ether copolymers or vinyl ester copolymers by saponification or hydrolysis, as well as polysaccharides of vegetable, animal, microbial or synthetic origin. Examples of polysaccharides include starch, cellulose, locust bean gum, dextran, guar gum, xanthan, xylan, pectin, alginate and chitin, as well as synthetic polydextrose. The use of starch and cellulose is preferred for commercial reasons. In addition, modified polysaccharides are preferably used because of the improved solubility. These are polysaccharides where the molecular weight has been modified by thermal, mechanical, enzymatic, oxidative or acid-catalyzed influence (reaction products), or those that have been transformed into derivatives by means of chemical modification, such as esterification, for-a-ring, hydrogenation and reglycosylation. Examples of these include white and yellow dextrins, maltodextrins, oxidized and acid decomposed starches, carboxymethyl starch, dialdehyde starch, cationic, anionic and neutral ethers and esters of cellulose and starch. Exceptions to this are sugars and sugar derivatives, as well as oligomers with 1 to 6 monosaccharide units, such as those described in the unpublished German patent application No. P-4 221 381.

According to the present invention, mixtures of the indicated polyhydroxy compounds with mono- or oligosaccharides or derivatives thereof can also be used as polyhydroxy compounds.

It is also possible that the polymers according to the present invention comprise derivatives with polyhydroxy compounds, and which are formed from the indicated polyhydroxy compounds and other components in the monomer mixture during the course of the manufacturing process.

Further derivatives of polyhydroxy compounds which can be advantageously used include sugar acids, such as glutaric acid, ascorbic acid or other polyhydroxy-carboxylic acids, such as dimethylhydroxypropionic acid, as well as esters of carboxylic acids or hydroxycarboxylic acids, e.g. citric acid esters of polyglycerol, sugar alcohols, sugar carboxylic acids, mono- and oligosaccharides, hydrogenated and/or chemically modified mono- and oligosaccharides, amino sugars, triethanolamine, tris-hydroxyethylmelamine.

Further polyhydroxy compounds which can be used include mono- or di-fatty acid esters of polyhydroxy compounds, such as glycerol, polyglycerol, of derivatives of hydrogenated sugar types, anhydro compounds, e.g. sorbitan or anhydrosorbitol. Examples of such include sorbitan monooleate, sorbitan palmitate, sorbitan stearate or isostearate, sorbitan laurate, sorbitan sesquioleate, polyoxyethylene oleate, polyoxyethylene and polyoxypropylene sorbitol, and triglycerol monolaurate and triglycerol stearate.

It is often advantageous to use polysaccharides which exhibit a combined modification of molecular weight reduction and chemical modification, or to use mixtures of different polyhydroxy compounds.

Suitable monoethylenically unsaturated C3 to C10 monocarboxylic acids mentioned under A) include acrylic acid, vinylacetic acid, 3-vinylpropionic acid, methacrylic acid, crotonic acid, dimethylacrylic acid, 2-pentenoic acid, 3-hexenoic acid and 2-hexenonic acid, alkali and/or ammonium - and/or the amine salts thereof, as well as corresponding mixtures. Methacrylic acid, acrylic acid and vinyl acetic acid are preferred, with acrylic acid and methacrylic acid being particularly preferred.

Among the sulfonic acid-containing monomers and the monoethylenically unsaturated sulfuric acid esters mentioned in group B), the following are particularly preferred: Vinyl, allyl and metallyl sulfonic acid and acrylamidomethylpropane sulfonic acid, styrene sulfonic acid, as well as sulfuric acid esters of hydroxyethyl (meth)acrylate or of olefinically unsaturated alcohols, e.g. allyl and metallyl sulfate and/or the alkali and/or ammonium and/or amine salts thereof.

The monomers mentioned under C) are: polyglycol ethers and polyglycol esters and/or esters of (meth)-acrylic acid and (meth)-allyl alcohol, which may optionally have an end group on one end. Examples of these include an allyl alcohol etherified with 10 moles of ethylene oxide and a methoxypoly(ethylene glycol) methacrylate with 20 ethylene oxide units.

Because of their functionality, the monomers have mentioned

under D) a molecular weight increasing property. This is achieved by a higher degree of polymerization or by branching and cross-linking. Suitable monomers are thus those that are easily polymerizable, as well as those that have two or more ethylenic double bonds that act as bifunctional crosslinkers.

agents, or monomers with an ethylenically unsaturated double bond and another functional group. Examples of such are acrylamide, allyl methacrylate and glycidyl methacrylate.

Examples of monomers according to E) include: Alkyl and/or hydroxyalkyl(meth)-acrylic esters, mono- and dialkyl esters of maleic acid, as well as N-alkyl- and N,N-dialkyl-(meth)-acrylamide and vinyl carboxylic acid esters, f .ex. methyl-, ethyl- and butyl(meth)-acrylates, the corresponding hydroxy-ethyl-, -propyl-, -butyl-(meth)-acrylates, N-methyl-, N-dimethyl-, N-tert-butyl - and N-octadecyl-acrylamide, maleic acid mono- and diethyl esters, as well as vinyl acetate and vinyl propionate, on the condition that the copolymers produced are water-soluble.

The above listing of the particular polyhydroxy compounds and the particular monomers is illustrative only and should not be construed as limiting.

The polymers according to the present invention can be obtained in solution or suspension according to polymerization methods which are known per se.

The polymerization of the monomers is preferably carried out in aqueous solution. The polymerization is initiated using polymerization initiators that dissociate into radicals. Redox systems and thermally decomposing radical generators or combinations thereof may be used, including catalyst systems which may be initiated by radiation.

Above all, the peroxides are suitable initiators, with hydrogen peroxide, t-butyl hydroperoxide, peroxy disulphates and combinations thereof being preferred. The initiators are combined with reducing agents which are known per se, e.g. sodium sulphite, hydrazine, heavy metal salts and others. Depending on the polymerization performance, the initiator system can be added continuously or in portions or with alternating pH values. The molecular weights can be influenced in a known manner by means of regulators, such as mercapto compounds.

The graft copolymerization can be carried out under adiabatic or isothermal conditions, the reaction being carried out so that part of the monomer mixture is produced, the polymerization is started and the monomer mixture is then measured. The poly-hydroxy component is then either added in its entirety to the pre-mixed material, or dosed together with the monomer mixture, or a part of this is prepared and the other part is dosed. The temperature during the copolymerization can vary within a wide range. This range is between 0°C and 200°C. Depending on the initiators to be used, optimal temperatures can be between 10°C and 150°C, preferably between 20°C and 120°C. It is possible to carry out the polymerization at the boiling point of the solvent at reduced or increased pressure.

Polymerization under adiabatic conditions is preferred. In that case, it is suitable to start the polymerization at low temperatures, e.g. at 25°C. The final temperature reached due to the released heat of polymerization depends on the monomers used and on the concentration conditions, and at an adequate pressure can be e.g. up to 180°C.

During the copolymerization, the pH value of the reaction mixture can vary within wide ranges. It is advantageous to carry out the copolymerization at low pH values, e.g. so that the acrylic acid used is not or only partially neutralized in advance and that adjustment to neutrality (pH 7-8) is only carried out at the end of the polymerization if this is necessary. If polysaccharides are used, the final neutralization can cause discolouration of the polymer. This can be prevented by neutralizing the acidic monomers before the polymerisation. The behavior of the monomers during the copolymerization must always be ensured by the pH adjustment.

The graft copolymers according to the present invention can be produced by a continuous or discontinuous process. Production and properties of the graft copolymers according to the present invention will be illustrated in the following examples. It must be shown in particular that the polymers according to the present invention - in comparison with prior art - both have excellent hydrophilic suspension capacity and an increased binding capacity for multivalent cations and that they also cause a significant retardation of the precipitation of insoluble calcium and magnesium salts.

The graft copolymers according to the present invention can be used as dispersing agents and as complexing agents. They bind polyvalent metal ions in water-soluble complexes. They serve to inhibit water hardness. They are aids and components in detergents, cleaning agents and washing solutions and dye baths, and in particular they are excellently suitable as co-builders.

The graft copolymers according to the present invention have good biodegradability and can be excellently used in textile detergents, washing-up agents, agents for removing limestone and coatings in boilers, as water treatment agents and as textile auxiliaries. The graft copolymers can be used in aqueous solution, as a powder or as a granule.

The following table indicates the usual amounts (% by weight) of the graft copolymers used in detergents and cleaning agents.

By way of examples - purely illustrative, but not limiting - formulations for detergents and cleaning agents can be stated:

The products according to the invention can be advantageously used as aids when finishing textiles or textile materials, e.g. by boiling or boiling cotton, where they bind the hardening substances and disperse the accompanying substances of cotton or impurities, and prevent their redeposition and support the effect of surface-active agents. The polymers according to the present invention are used as stabilizers in hydrogen peroxide bleaching, and if stabilizing silicates are also used, they prevent silicate deposits.

The polymers according to the present invention can also be used as auxiliaries in washing and dyeing liquids for continuous and discontinuous use, thereby removing the non-fixed color and achieving good resistance to washing, water and the washing off of excess color (crocking) or rubbing . In the case of polyester fibers, the dispersing action of the polymers causes separation of oligomeric polyester components which dissolve and interfere with the dyeing process.

When it comes to dyeing cellulose, the polymers according to the present invention promote the solubility of reactive dyes and of direct dyes and result in improved leveling (leverness) of the dye on the fibers, especially if larger amounts of salt are present in the liquid. In dye vats, they can be advantageously used as a pasting agent for dye or as a dispersant in the pigmentation bath. In the case of sulfur dyeing, they support the dispersion of the dye and prevent bronzing.

When dyeing synthetic fibres, the polymers according to the invention prevent the formation of agglomerates of dispersed dyes, so that deposits in the cones are prevented.

When dye vat colors and prints are washed off, the polymers according to the invention bind non-fixed dye components and redeposition is reduced to a considerable extent. Due to the increased dye diffusion into the washing liquid, the polymers ensure optimal removal of non-fixed colors while saving water and energy. For this reason, the products according to the present invention represent an effective substitute for polyphosphates in the post-treatment of naphthol-dyed products; when reactive pressures are washed off, precipitation of calcium alginate is prevented.

The dispersing and complex-forming effect of the polymers according to the present invention is effective without heavy metal compounds being remobilized, both from dye chromophores (reactive dyes and metal complex dyes) and from water-insoluble deposits of natural

or industrial nature.

The quantities that are necessary can in practice be reduced by a quantity that is approx. three to five times less than that required if conventional aids, such as polyacrylates, are used.

The polymers according to the present invention can be used in combination with surfactants, especially anionic surfactants, in non-neutralized form (as acid regulators) in combination with complex-forming organic acids, such as citric acid, lactic acid, gluconic acid and phosphonic acids and surfactants, especially

anionic surfactants.

Such combinations are, for example, advantageously used instead of the conventional multi-stage pre-treatment carried out in separate baths, for example to treat high load cotton or linters, including the steps of acid extraction, chlorite bleaching, boiling and H 2 O 2 bleaching, this being carried out in such a way that the pre-treatment is carried out in just one adjustable treatment bath with the addition of the polymers according to the present invention.

This method according to the present invention can also be used in continuous processes. The methods prevent the formation of unwanted organic halogen compounds and environmental impacts in connection with such.

The polymers are suitable additives for removing glue from glue-bound fibers (desize fiber sizes) that are sensitive to

water hardness, e.g. polyester glue.

In leather production, the polymers according to the present invention result in increased chromium absorption through the leather during the chrome tanning, and in retanning they contribute to properties in terms of the fullness and softness of the leather.

Due to the dispersing properties and the properties for complexing heavy metals, but not remobilizing properties, the polymers according to the present invention can advantageously also be used as aids in papermaking, e.g. in the bleaching of cellulose and other fibrous materials, in the production of dispersions of pigments and fillers, such as kaolin, calcium carbonate, satin white, talc, titanium dioxide, aluminum hydroxide and barium sulphate, as well as in the production of coating colours. In such cases, filler and pigment slurries, as well as coating colours, have a high solids content and good storage stability is achieved.

The polymers according to the invention can be used in combination with other aids.

Due to the fact that the polymers according to the present invention have a high effect which results in low dosages, and a good biological degradability, the products are to a high degree ecologically acceptable.

The polymerization reactions carried out in the following examples and comparative examples were carried out in a 2 liter reaction flask, equipped with stirrer, reflux condenser, thermometer and measuring devices for liquid and gaseous substances.

Example 1

In the polymerization reactor, the following components are mixed and then cooled to 15°C: 248.9 acrylic acid, 133.2 g distilled water, 64.0 g 50% sodium hydroxide solution, 64.5 g sodium metalyl sulfonate, 201.8 g of a 25% aqueous solution of Mowiol 5-88 (polyvinyl alcohol from Hoechst) and 107.6 g of a 60% aqueous solution of methoxy polyethylene glycol methacrylate (20 mol EO). The polymerization is started by adding 20 mg of iron (II) sulfate, dissolved in 17.8 g of distilled water, 4.0 g of sodium disulphite and 5 g of tert-butyl hydroperoxide (70%), dissolved in 17.8 g of distilled water . Within 2 minutes the temperature rises to 65°C. The temperature is then increased to 65°C by means of a heating bath, and the dosage of a second initiator system consisting of the components 17 g of t-butyl hydroperoxide (70%), dissolved in 66.7 g of distilled water, and 10 g of sodium disulfite , dissolved in 66.7 g of distilled water, is started over a time period of 1.5 hours. When dosing is complete, stirring is continued for another 30 minutes, followed by cooling and neutralization with 163.6 g of 50% sodium hydroxide solution. The polymer has a dry matter content of 43.1% and a cloudy appearance; in this state the turbidity is stable and disappears on dilution. The residual content of acrylic acid amounts to 20 ppm and the residual content of metallyl sulphonate 0.2%, and the average molecular weight Mw is 29128.

Example 2

212.1 g of acrylic acid, 200.0 g of distilled water, 75.0 g of sodium metalyl sulphonate, 54.5 g of 50% sodium hydroxide solution and 150.0 g of triglycerol are placed in the polymerization vessel, and at a temperature of 24°C, 5.9 g of mercaptoethanol, 26 mg of iron (II) sulfate, dissolved in 10 g of distilled water, and 4 g of hydrogen peroxide (35%), dissolved in 10 g of distilled water. The polymerization starts spontaneously, and the temperature reaches 101°C after 4 minutes and falls again. At a temperature starting from 75°C, a second initiator system consisting of 10.7 g of sodium persulfate, dissolved in 50 g of distilled water, and 10.7 g of sodium disulphite, dissolved in 50 g of water, is measured over a time period of 1.5 hours. At the end of the dosage, stirring is continued for 30 minutes, followed by cooling and neutralization with 139.4 g of 50% sodium hydroxide solution. The colourless, clear end product has a pH value of 5.8 and a dry matter content of 52.8%, the residual content of acrylic acid amounts to 15 ppm and the average molecular weight Mw is 5907.

Example 3

Example 2 is repeated, with the exception of the initiators. The start of the polymerization is initiated with 20 mg of iron (II) sulfate, dissolved in 10 g of distilled water, 3 g of sodium disulphite and 4 g of t-butyl hydroperoxide (30%), dissolved in 10 g of distilled water, as the temperature rises from 20 °C to 98°C. The second initiation which must be carried out as in example 1 consists of 12 g of t-butyl hydroperoxide (70%), dissolved in 50 g of distilled water, and 9 g of sodium disulfite, dissolved in 50 g of distilled water.

The end product is a clear, colorless solution with a dry substance content of 51.4% and a residual acrylic acid content of 10 ppm, and the average molecular weight Mw is 11480.

Example 4

Example 1 is repeated, with the exception that the polyvinyl alcohol solution is replaced by 50.4 g of triglycerol and that the amount of water is increased to 284.6 g.

The clear, colorless final product has a solids content of 43.2%, a residual acrylic acid content of <10 ppm and a residual methallyl sulfonate content of 0.16%. The average molecular weight Mw is 23540.

Example 5

As a modification of example 4, the content of triglycerol was increased to 194.6 g and the initiation is carried out as follows: Start of the polymerization with 10 g of mercaptoethanol, 30 mg of iron (II) sulfate and 6 g of sodium disulfite, dissolved in 17.8 g of distilled water , and 8 g of t-butyl hydroperoxide (70%), dissolved in 17.8 distilled water. The second initiation to be carried out as in example 1 was carried out with 14 g of sodium persulphate, dissolved in 66 g of distilled water, and 10 g of sodium disulphite in 66 g of distilled water.

The clear, colorless final product had a solids content of 50.3%, a residual acrylic acid content of 10 ppm and a metallyl sulfonate content of 0.3%. The average molecular weight Mw is 3470.

Example 6

As a modification of example 3, the triglycerol is replaced with 150.8 g of the starch dextrin maltodextrin MD 20 (from Avebe), and the initiation of the beginning of polymerization is carried out after the addition of 10 g of mercaptoethanol with 20 mg of iron (II) sulfate and 3 g of sodium disulfite, dissolved in 10 g of distilled water, and 4 g of t-butyl hydroperoxide (70%), dissolved in 10 g of distilled water. In the initiation to be carried out as in example 1, 10 g of sodium persulphate and 10 g of sodium disulphite are used, each of which is dissolved in 50 g of distilled water.

The final product is a clear solution with a solids content of 54.7% and a residual acrylic acid content of <20 ppm. The average molecular weight Mw is 2996.

Example 7

212 g of acrylic acid, 284 g of distilled water, 54.5 g of 50% sodium hydroxide solution, 194.6 g of maltodextrin MD 20 (starch dextrin from Avebe) and 75 g of sodium metalyl sulphonate are dissolved together; at 15°C, 20 mg of iron (II) sulfate and 4 g of sodium disulfite, dissolved in 17.8 g of distilled water, and 5 g of t-butyl hydroperoxide (70%), dissolved in 17.8 g of distilled water, are added. Within 4 minutes the temperature rises to 70°C, and the second initiation starts over a time period of 1.5 hours, this consisting of solutions of 14 g of sodium persulphate and 10 g of sodium sulphite, each in 66 g of distilled water. Stirring is then carried out for 30 minutes and neutralization with sodium hydroxide solution is carried out after cooling. The slightly cloudy polymer has a solids content of 49.9%, a residual content of acrylic acid of <20 ppm and of methallyl sulphonate of 0.18%. The average molecular weight Mw is 26225.

Example 8

Example 3 is repeated, with the modification that 2 g of allyl glycidyl ether is additionally used in the formulation and that 12 g of sodium persulfate and 10 g of sodium disulfite, each dissolved in 50 g of distilled water, are used in the second initiation step to be carried out as in example 1.

The colorless, clear polymer has a solids content of 52.8% and a residual acrylic acid content of <20 ppm. The average molecular weight Mw is 14872.

Comparative example 1

(according to DE-3 714 732 C2, example 2)

108 g acrylic acid is neutralized with 300 g 20% sodium hydroxide solution. 91 g of glucose are dissolved in 100 g of water and mixed with 49 g of 35% H2C>2 solution. 100 g of water is heated to 85°C in the reaction vessel, and the acrylic acid and glucose solution are added over 90 minutes, the pH value being kept at 9.0. 10 minutes after the addition has ended, the temperature in the reaction vessel suddenly rises to 103°C and the polymer discolours to yellow. Cooling is then carried out. The polymer solution has a solids content of 3 0.6% and a viscosity of 220 mPa-s. By adding hydrochloric acid can

the polymer precipitates in the form of a slimy precipitate that is difficult to separate.

Comparative example 2

(according to DE-4 003 172 A1, example 21)

243 g of water, 160 g of sucrose, 47.9 g of maleic anhydride, 0.57 g of phosphoric acid and 2 g of sodium hydrogen sulphite are placed in the reaction vessel and stirred for 1 hour at 80° C. in a stream of nitrogen. Then 70.5 g of 70% sodium hydroxide solution is added slowly to this mixture, and a solution of 133.6 g of acrylic acid in 141.9 g of water is measured over a period of 5 hours at 80°C, and solutions of 8.1 g 35% hydrogen peroxide in 37.6 g of water and 2.85 g of sodium sulfate in 40 g of water are added evenly over a period of 6 hours. The batch then undergoes a final heat treatment for 2 hours. The polymer solution has a solids content of 37.7% and a viscosity of 155 mPa-s.

Comparative example 3

(according to DE-4 003 172 A1, example 25)

290 g of maltodextrin MD 14 (dextrose equivalent value 14, from Avebe), 470 g of water, 4.2 ml of 0.1% aqueous solution of ferric ammonium sulfate, 101.4 g of maleic anhydride and 74.5 g of sodium hydroxide are placed in the reaction vessel and heated to boiling. When boiling starts, a mixture of 120 g of acrylic acid and 132.7 g of a 50% aqueous solution of the sodium salt of acrylamidomethylpropanesulfonic acid is added over a period of 5 hours, and 80 g of 30% hydrogen peroxide and a solution of 24 g of sodium persulfate in 72 g of water is dosed over the course of 6 hours, with the temperature being maintained so that the mixture boils. After completion of the last initiator dosing, a final heat treatment is carried out for 1 hour. Neutralization is then carried out with 155 g of 50% sodium hydroxide solution. A cloudy, brown solution is obtained, which has a solids content of 45.2% and a viscosity of 560 mPa-s. During a time period of 14 days, a precipitate has settled from the cloudy solution.

Example 9 - Determination of the resistance to hard water

To a test water with 33.6°dH (= German water hardness) (pure calcium hardness) a certain amount of 10% solution of graft polymer was added; it was boiled for 5 minutes on a hot plate and then judged optically for clarity, opalescence and turbidity. By varying the amount of copolymer, the concentration of grams of product (dry substance) per liter of hard water, i.e. the concentration at which, after an initial turbidity/opalescence, a clear solution appears for the first time.

The results shown in table 1 make it clear that with the polymers according to the invention an effective and improved inhibition of scale or similar deposits or prevention of precipitation of components in the hard water can be achieved.

Example 10 - Determination of the calcium binding capacity

The capacity for binding calcium is determined according to the so-called Hampshire test, where the polymer is titrated with a calcium acetate solution in the presence of carbonate ions. The final value for the titration is expressed in mg CaC03/<g> polymer.

Procedure: 1 g of complexing agent (polymer according to the invention or comparative product) is dissolved in 50 ml of distilled water, neutralized with sodium hydroxide solution, and 10 ml of 2% sodium carbonate solution is added to this. It is filled up to 100 ml, and the pH value is adjusted to 11.0. Titration is carried out with 0.25 ml of calcium acetate solution until a persistent and clear turbidity/precipitation occurs. The stage before turbidity is indicated by a slight opalescence, the transition being either narrow or wide, depending on the complexing agent. The complexing power for some of the polymers according to the present invention is so high that no turbidity occurs, apart from an opalescence.

The polymers according to the present invention exhibit very high values for the calcium binding force. If maleic anhydride (comparative examples 2 and 4) is additionally used, or in the absence of sulfonic acid group-containing monomers (comparative example 1), polymers with a reduced calcium-binding capacity are obtained.

Example 11 - Determination of the hydrophilic suspending capacity

The dirt-carrying capacity of building materials can be characterized by determining the hydrophilic suspension capacity. As a measure of the dirt-bearing capacity, the suspending capacity for powdered iron oxide is used in this context. Determination of the suspending power takes place by photometric turbidity measurement of a suspension consisting of the test substance, an iron oxide pigment and the surfactant Marion A (alkylbenzene sulphonate). In a shaking cylinder, the iron oxide is shaken intensively in an aqueous solution of the test substance while adding Marion A, and after 24 hours the intensity of the still existing turbidity is determined by photometry. The extinction E450 is measured at 450 nm in a 1 cm cuvette.

The measured extinction values represent target figures for the hydrophilic suspending capacity. Products with high suspending activity stabilize the pigments in the aqueous phase and exhibit high extinction values.

Example 12 - Lime deposit conditions in a washing test

In a household washing machine, cotton fabric was washed with a detergent formulation comprising 10% by weight polymer dry substance as a builder. After 12 washings at 90°C with water with a hardness of 13°dH, the residual ash content of the fabric was determined. A commercial product of maleic acid/acrylic acid (30/70% by weight) was used as a comparison polymer. The inhibition of redeposition was determined in a Linitest laboratory washer.

Composition of the washing powder:

Example 13 - Washing colored material

Application of the polymers according to the invention is exemplified by means of a discontinuous washing of a cotton fabric which has undergone reactive dyeing.

First, the coloring liquid is drained off, followed by

1. rinsing with overflow at 60°C for 10 minutes,

2. rinsing in a fresh bath at 90°C for 10 minutes,

3. standing with 1 g/l polymer according to example 5 at 90-95°C for 10 minutes,

rinsing at 45°C for 15 minutes.

The cotton fabric has an intensive colour, shows no fading and shows good washing fastness.

The above time periods, temperatures and sequences are intended to be illustrative. The polymers according to the present invention can also be used under other washing conditions.

Example 14 - The ratio of dispersants in liquids with high alkalinity

Test solutions (500 ml liquid) of water with 24°dH, 10 g/l NaOH and the polymer according to the present invention are heated to boiling temperature, held at this temperature for 15 minutes and cooled. The liquid loss is compensated by the addition of water (20°dH).

Table 6 indicates the appearance of the solutions depending on the amount used and in comparison with commercial products I, II and III: I: Sequion MC 200, alkylphosphonate, commercial product from

Bozzetto, Italy.

II: Varsaquest DC-N, polyacrylate, commercial product from DeJonge, Belgium.

III: Lavoral S 313, sodium salt of a polyacrylic acid, commercial product of Chemische Fabrik Stockhausen, GmbH, Krefeld, Germany.

Clear solutions are obtained if quantities starting from:

3 g/l with I

2 g/l with II

1 g/l with III

1 g/l polymer according to example 5.

Example 15

Rep of raw cotton is boiled with 5 ml of acetic acid with a liquid ratio of 1:10 for 30 minutes. Then 200 ml of the liquid is cooled to 60°C and each of the following is added: 0.5 g/l, 1.0 g/l and 2 g/l polymer according to ex. 5, 0.05 g/l indanthrene blue BC Coll

20.0 ml/l NaOH, 50%, and

5.0 g/l hydrosulphite, concentrated.

After a residence time of 15 minutes (at 60°C), the liquid was sucked off using a "blue band filter".

The polymers exhibit a good dispersing effect; in the concentrations used, they prevent precipitation of flocculated constituents.

Example 16

At a liquid ratio of 1:20 and a temperature of 70-80°C, black colored PES flakes were treated with a liquid containing 1 g/l polymer according to example 5 and 1 g/l Solopol DP (fatty amine ethoxylate, trade name of Chemische Fabrik Stockhausen, GmbH, Krefeld) for 20 minutes, and then underwent hot and cold rinsing. Oligomers, dye and fiber dust were removed from the fibers.

Example 17

Bleaching of 100% cotton linters with a whiteness degree of 29.5 (according to Elrepho) was carried out in a bath with a liquid ratio of 1:20 for each, and included the following treatment steps:

Step 1 Treatment with a liquid of

1 ml/l HC1, conc. (37%)

2 ml/l of a combination comprehensive

42.0 parts of the polymer according to the present invention according to example 5 by acidic final adjustment 10.0 parts lactic acid

25.0 parts gluconic acid

4.0 parts phosphonic acid

14.0 parts of a C12-C18 fatty alcohol polyglycol ether sulfate, and

5 parts of an antifoam EO-PO block polymer

was carried out at 25°C within 30 minutes.

Step 2 A) Treatment with a liquid of

10 ml/l NaOH, 50%

2 g/l Lavoral S313 (commercial product from

Chemische Fabrik Stockhausen GmbH)

45 minutes at 95°C

B) Treatment with a liquid of

10 ml/l NaOH, 50%

2 g/l of the combination according to step 1

45 minutes at 95°C

C) Treatment with a liquid of

10 ml/l NaOH, 50%

2 g/l of the combination according to the invention in example 5

was performed during 45 minutes at 95°C

Step 3 Treatment with a liquid of

3 ml/l of the combination according to step 1

8 ml/l hydrogen peroxide, 3 5%

was performed during 45 minutes at 95°C. The hydrogen peroxide had previously been diluted in a solution of the combination according to step 1 and a portion of water and added slowly while warm.

The liquid is drained off and the material is hot-rinsed at 80°C while adding 2 ml/l polymer according to example 5.

The degree of whiteness for several samples was between 69 and 70%.

Example 18

At a temperature of 10°C, 20 mg of ferrous sulfate and 4 g of sodium disulfite and 5 g of t-butyl hydroperoxide (70%) each dissolved in 17.8 g of water were added to a mixture of 334.6 g of distilled water , 248.9 g of acrylic acid, 50.4 g of tartaric acid, 64.5 g of sodium metalyl sulfonate and 107.6 g of methoxy polyethylene glycol methacrylate (20 mol EO) (60% solution in water). The temperature rises to 53°C due to the incipient polymerization reaction. The temperature is raised to 70°C by means of a heating bath, after which two solutions of 14 g of sodium persulphate and 10 g of sodium disulfite, each in 50 g of water, are added dropwise over a period of 1 hour. At the end, the polymer is neutralized with a 50% sodium hydroxide solution. The clear polymer solution has a solids content of 42.2% and a viscosity of 720 mPa-s.

Example 19

As a modification of Example 4, 56.1 g of sodium gluconate was used instead of triglycerol and the amount of water was increased to 334.6 g. The polymerization was initiated at 15°C by the addition of 20 mg of iron (II) sulfate, 4 g sodium disulfite and 5 g of t-butyl hydroperoxide (70%), each dissolved in 17.8 g of distilled water. After the temperature had reached 62°C, it was raised to 73°C by means of a heating bath, and the dosing of 17 g of t-butyl hydroperoxide (70%) and 10 g of sodium disulfite, each dissolved in 50 g of water, was started over a time period of 1 hour. After completion of the polymerization, neutralization was carried out with 50% sodium hydroxide solution. The end product is a clear solution with 42.8% dry matter, and the resistance to hard water amounts to 0.5 g solids/l.

Example 20

As a modification of Example 19, 50 g citric acid ester of polyglycerol was used instead of 56.1 g sodium gluconate. The citric acid ester had been prepared by direct condensation of 0.3 mol of polyglycerol with 1.5 mol of citric acid (according to PCT/EP92/00512, p. 12, ex. 1), the resulting water of condensation being removed by azeotropic distillation.

Example 21

As a modification of Example 4, the triglycerol was replaced by glycerol. Initiation of the polymerization was carried out after the addition of 10 g of mercaptoethanol and 30 mg of iron (II) sulfate at 15°C with the help of 8 g of t-butyl hydroperoxide (70%) and 6 g of sodium disulfite, each dissolved in 17.8 g of water . After a temperature increase to 100°C, the mixture was allowed to cool to 78°C and then two solutions of 17 g of t-butyl hydroperoxide (70%) and 10 g of sodium disulfite, each dissolved in 66 g of water, were added over the course of 1 hour. After cooling, neutralization was carried out with 50% sodium hydroxide solution. The end product is a clear solution with 44.1% dry matter and a resistance to hard of 0.5 g solids/l.

Example 22

As a modification of Example 21, the amount by weight of sodium metalylsulfonate was replaced by acrylamidopropanesulfonic acid and the amount of mercaptoethanol was reduced to 2 g. %) .

The final product was a clear solution with a solids content of 42.5% and a resistance to hard water of 0.5 g solids/l.

Example 23

180 g of distilled water, 124.4 g of acrylic acid, 32 g of 50% sodium hydroxide solution, 303.5 g of 41% acrylamide solution, 64.5 g of sodium metalyl sulfonate, 46.2 g of glycerol and 107.5 g of a 60% solution of methoxy polyethylene glycol methacrylate (20 mol EO) are dissolved together, and then 20 mg of iron (II) sulfate and 4 g of sodium disulfite, dissolved in 17.8 g of water, and 5 g of t-butyl hydroperoxide (70%), dissolved in 17.8 g are added water. The temperature rises from 15°C to 100°C and falls again. At an initial temperature of 75°C, 17 g of t-butyl hydroperoxide (70%) and 10 g of sodium disulfite, each dissolved in 50 g of water, are measured over the course of 1 hour. After the polymerization has ended, neutralization is carried out with sodium hydroxide solution. The polymer has a dry substance of 42.1%, a viscosity of 280 mPa-s and a resistance to hard water of 0.5 g solids/l.

Example 24

250.2 g of acrylic acid, 64.3 g of sodium hydroxide solution (50%), 88.5 g of sodium metalyl sulphonate and 176.9 g of glycerol are dissolved in 281 g of distilled water. 6.95 g of mercaptoethanol and 0.0312 g of iron (II) sulfate are then added. The temperature is set to 18°C and the polymerization is started by adding 4.72 g of hydrogen peroxide (35%). After 10 minutes, the maximum temperature of 96°C is reached; the mixture is allowed to cool to 75°C, and at this temperature two solutions of 12.6 g of sodium persulphate in 59 g of water and 2.5 g of sodium disulphate in 59 g of water are dosed. Cooling and neutralization with 163.3 g of sodium hydroxide solution (50%) is carried out at the end. The polymer has a clear colour, a dry matter content of 46.2%, a pH value of 5.7 and a viscosity of 240 mPa-s.

Example 25

A polymer was prepared from 50% by weight sodium acrylate, 15% by weight sodium metalyl sulphonate, 5% by weight methoxy polyethylene glycol methacrylate and 30% by weight glycerol. The colorless, clear, aqueous polymer solution had a solids content of 45.8%, a viscosity of 133 mPa-s and a pH of 5.5.

Example 26

A polymer was built up of 76.1% by weight acrylic acid, 15.7% by weight sodium metalyl sulphonate and 8.2% by weight glycerol. The aqueous, colorless and light polymer solution had a pH value of 5.5, a dry matter content of 42.8% and a viscosity of 117 mPa-s.

Example 27 - Peroxide stabilization in bleaching liquids

The stabilizing effect of complexing agents against the liquid will be tested in this experiment. Amounts of minerals that correspond to a medium cotton fabric and a sequestering agent, respectively. a complexing agent was added to the liquid. The bleaching liquid was prepared in soft water with the following additives: 1.0 g/l wetting agent (mixture of isotridecyl alcohol ethoxylate and alkane sulphonate)

0.2 g/l magnesium chloride

1.0 g/l stabilizer

4.0 ml/l sodium hydroxide solution (50%)

8.0 ml/l hydrogen peroxide (35%)

The content of residual peroxide is determined permanganometrically after certain periods/temperatures which are indicated in the following table. Batches with stabilizers for the polymer according to example 1 according to the present invention, with water-glass (according to the state of the art) and a blank test without stabilizers are compared. The good peroxide-stabilizing property of the polymer according to the present invention can be seen:

Example 28 - Chromium depletion during leather production

In chrome tanning, the chrome salt is fixed on the leather in the presence of polymers. The success of the chrome tanning is confirmed by a high chrome absorption through the leather and a high shrinking temperature for the leather. Chromium absorption in the leather is determined indirectly by the chromium salt that remains in the liquid and is indicated as depletion (exhaustion). The shrink temperature means the temperature at which the leather begins to shrink. The following table shows the chromium content of the tanning liquid, how much has been used up on this basis and the shrinking temperature. A commercial acrylic acid/- DIMAPA copolymer serves as a comparison:

With the help of the polymers according to the invention, a very high proportion of the chromium salt is fixed in the liquid in the leather, and the chromium depletion must be considered very good.

Example 29 - Re-tanning of leather

Leather properties, such as softness, grain density, smoothness, are affected by retanning. The following table shows the results of a retanning test with polymers according to the present invention and with the commercial product from example 28 used as a comparison. Skin from cattle ("wet blue", 1.8-1.0 thinly sliced substance = shaved substance) was used. The assessment of the best results is in the range 1-5, where 1 represents the best value.

present invention and with the commercial product from example 28 used as a comparison. Skin from cattle ("wet blue", 1.8-1.0 thinly sliced substance = shaved substance) was used. The assessment of the best results is in the range 1-5, where 1 represents the best value.

Claims (29)

1. Water-soluble graft copolymers of polyhydroxy compounds, reaction products thereof and/or derivatives thereof, with the exception of mono- and disaccharides and oligosaccharides have an average degree of polymerization of from 1.1 to 20 sorbitol, tartaric acid and gluconic acid, and a monomer mixture, characterized in that it has been obtained by free-radical graft copolymerization of a monomer mixture consisting of A) 45-96% by weight of at least one monoethylenically unsaturated C3-C10 monocarboxylic acid and/or at least one salt of such a monocarboxylic acid with a monovalent cation, B) 4-55% by weight of at least one monoethylenically unsaturated, sulfonic acid group-containing monomer, one monoethylenically unsaturated sulfuric acid ester, and/or vinylphosphonic acid and/or at least one salt of these acids with monovalent cations, C) 0-30 weight % of at least one water-soluble, monoethylenically unsaturated compound modified with 2-50 mol of alkylene oxide per mol, D) 0-45% by weight of at least one additional water-soluble, free-radically polymerizable monomer; E) 0-30% by weight of other free-radically polymerizable monomers that are slightly soluble or insoluble in water, the sum of A to E being 100% by weight, by avoiding decarboxylating monomers, in the presence of polyhydroxy compounds and/or reaction products thereof and/or derivatives thereof and/or mixtures thereof, wherein the content of the polyhydroxy compounds and/or derivatives thereof and/or their reaction products in the total mixture amounts to 1-60% by weight, preferably 5-40% by weight and most preferably 5-30% by weight. 2. Graft copolymers according to claim 1, characterized in that they comprise polysaccharides such as polyhydroxy compounds, preferably starch, starch breakdown products and starch derivatives, cellulose, cellulose breakdown products and/or cellulose derivatives. 3. Graft copolymers according to claim 1, characterized in that they comprise polyvinyl alcohol and/or partially saponified polyvinyl acetates and/or partially hydrolyzed polyvinyl ethers as polyhydroxy compounds. 4. Graft copolymers according to claim 1, characterized in that they comprise glycerol and/or polyglycerols as polyhydroxy compounds, especially diglycerol, triglycerol and monoisopropylidene-diglycerol or monoisopropylidene-triglycerol. 5. Graft copolymers according to claim 1, characterized in that they as monomers A comprise acrylic acid and/or methacrylic acid, alkali/ammonium salts thereof and/or amine salts thereof. 6. Graft copolymers according to claim 1, characterized in that they as monomers B comprise allylsulfonic acid, metallylsulfonic acid, acrylamidomethylpropanesulfonic acid, vinylsulfonic acid, sulfatoethyl (meth)acrylate, vinylphosphonic acid and/or the salts of these acids with monovalent cations. 7. Graft copolymers according to claim 1, characterized in that they comprise allyl alcohol or the esters of unsaturated carboxylic acids, such as acrylic acid or methacrylic acid where the alcohol component has been modified with alkylene oxide, such as the water-soluble, monoethylenically unsaturated compounds modified with alkylene oxide. 8. Graft copolymers according to claim 1, characterized in that they as monomer D comprise molecular weight-increasing monomers, preferably those which have several monoethylenically unsaturated double bonds and/or those which have one ethylenically unsaturated double bond and one further functional cross-linking group. 9. Graft copolymers according to claim 1, characterized in that they comprise as monomer E alkyl and/or hydroxyalkyl(meth)acrylic acid ester, mono- and/or dialkyl esters of maleic acid, N-alkyl- and/or N,N-dialkyl (meth)-acrylamides and/or vinyl carboxylic acid esters. 10. Method for producing graft copolymers according to claims 1-9 of polyhydroxy compounds, reaction products thereof and/or derivatives thereof, and monoethylenically unsaturated monomers in solution or suspension at temperatures up to 200°C, using free radicals - polymerization initiators, characterized in that a total mixture is used which consists of 1-60% by weight, preferably 5-40% by weight and most preferably 5-30% by weight of polyhydroxy compounds, the reaction products and/or derivatives thereof, and 95-40% by weight of a monomer mixture which consists of A) 45-96% by weight of at least one monoethylenically unsaturated C3-C10 monocarboxylic acid and/or at least one salt of such a monocarboxylic acid with monovalent cations, B) 4-55% by weight of at least one monoethylenically unsaturated sulfonic acid group -containing monomer, one monoethylenically unsaturated sulfuric acid ester, and/or vinylphosphonic acid and/or the salts of these acids with monovalent cations, C) 0-30% by weight of at least one water-soluble, monoethylenically unsaturated compound modified with 2-50 mol of alkylene oxide per mol, D) 0-45% by weight of at least one further water-soluble, radically polymerizable monomer, E) 0-30% by weight of other radically polymerizable monomer substances that are slightly soluble or insoluble in water, the sum of A to E being 100% by weight, and for the polymerization the components in the total mixture of polyhydroxy components and monoethylenically unsaturated monomers are prepared either as a whole or in portions, and the remainder is measured or all components are measured. 11. Method for producing graft copolymers according to claims 1-9, of polyhydroxy compounds, reaction products thereof and/or derivatives thereof, and monoethylenically unsaturated monomers in solution or suspension at temperatures up to 200°C, using radical polymerization initiators, characterized in that polysaccharides, preferably starch, starch breakdown products and starch derivatives, cellulose, cellulose breakdown products and/or cellulose derivatives, are used as polyhydroxy compounds. 12. Method for producing graft copolymers according to claims 1-9 of polyhydroxy compounds, reaction products thereof and/or derivatives thereof, and monoethylenically unsaturated monomers in solution or suspension at temperatures up to 200°C, by means of radical polymerization -show initiators, characterized in that polyvinyl alcohol and/or partially esterified polyvinyl acetates and/or partially hydrolyzed polyvinyl ethers are used as polyhydroxy compounds. 13. Process for producing graft copolymers according to claims 1-9 of polyhydroxy compounds, reaction products thereof and/or derivatives thereof, and monoethylenically unsaturated monomers in solution or suspension at temperatures up to 200°C, using free radicals - polymerization initiators, characterized in that glycerol and/or polyglycerols, especially diglycerol, triglycerol and monoisopropylidene-diglycerol or monoisopropylidene-triglycerol are used as polyhydroxy compounds. 14. Use of the graft copolymers according to claims 1-9 for binding polyvalent metal ions. 15. Use of the graft copolymers according to claims 1-9 for inhibiting water hardness. 16. Use of the graft copolymers according to claims 1-9 as an additive and component in detergents and cleaning agents. 17. Use of the graft copolymers according to claims 1-9 as an additive and component in washing liquids. 18. Use of the graft copolymers according to claims 1-9 as an aid in textile finishing. 19. Use of the graft copolymers according to claims 1-9 as an aid in the pretreatment of raw fiber material or textiles. 20. Use of the graft copolymers according to claims 1-9 as aids for boiling, boiling and bleaching raw fiber materials, fibers and textiles. 21. Use of the graft copolymers according to claims 1-9 as an aid in dyeing natural and/or synthetic fibers or textiles. 22. Use of the graft copolymers according to claims 1-9 as an aid in textile printing, especially in reactive printing and vat colors for natural and/or synthetic fibers or textiles. 23. Use of the graft copolymers according to claims 1-9 as an aid in adhesive removal (desizing) from natural or synthetic fibers or textiles. 24.. Use of the graft copolymers according to claims 1-9 as an aid according to claims 18-23 in combination with surfactants, especially anionic surfactants. 25. Use of the graft copolymers according to claims 1-9 as an aid according to claims 18-24 in combination with complex-forming carboxylic acids. 26. Use of the graft copolymers according to claims 1-9 as an aid according to claims 19 and 20, 24 and 25, where they are used in chlorite-free bleaching, preferably in multi-stage processes and in adjustable treatment baths or in such continuous processes. 27. Use of the graft copolymers according to claims 1-9 for the production of pigment and dye dispersions. 28. Use of the graft copolymers according to claims 1-9 as an aid in paper production for the production of pigment and filler dispersions and for coating colours. 29. Use of the graft copolymers according to claims 1-9 as an aid in the production of leather.